CN108144627B - Biomass gas shift methanation bifunctional catalyst and preparation method thereof - Google Patents

Biomass gas shift methanation bifunctional catalyst and preparation method thereof Download PDF

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CN108144627B
CN108144627B CN201711274743.8A CN201711274743A CN108144627B CN 108144627 B CN108144627 B CN 108144627B CN 201711274743 A CN201711274743 A CN 201711274743A CN 108144627 B CN108144627 B CN 108144627B
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manganese
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CN108144627A (en
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金保昇
董新新
孙漪清
石坤
于磊
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Southeast University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas

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Abstract

The invention discloses a shift methanation catalyst and a preparation method thereof, wherein the catalyst comprises an active component, an auxiliary agent and a carrier; the active components comprise a first active component nickel and a second active component manganese; the mass percentage of the first active component nickel and the catalyst is 5-30% according to the mass of the metal element; the mass percentage of the second active component manganese to the catalyst is 1-10% according to the mass of the metal element; the assistant is rhenium, and the mass percent of the assistant and the catalyst is 0.2-1.5% by mass of the metal element. The catalyst has simple preparation method, and is especially suitable for low H2the/CO biomass fuel gas has higher conversion and methanation activity.

Description

Biomass gas shift methanation bifunctional catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a shift methanation catalyst and a preparation method thereof.
Background
The biomass fuel gas prepared by converting biomass solids such as straws into combustible gas by adopting a gasification technology has the characteristics of high utilization efficiency, wide application, good market prospect and the like, so that the biomass fuel gas can be used for town gas supply instead of the traditional fossil fuel. The method is used for town gas supply, can solve the problem of energy support in the process of rapid development of township and the environmental problem caused by extensive burning of straws, and has good economic and social benefits. Town gas has strict requirements on both heat value and CO content. Taking the national standard GB/T13612-2006 Artificial gas as reference, taking the heat value and the CO volume fraction as parameter requirements, and specifying the standard: first kind of gasThe heat value of the heat pump is required to be more than 14MJ/Nm3The CO content needs to be less than 10 percent; the heat value of the second kind of gas needs to be more than 10MJ/Nm3The CO content needs to be less than 20%. Biomass gas H varies according to raw material source, gasification medium and operation conditions2The variation range of the ratio of/CO is large. Especially for H2The low calorific value of the biomass fuel gas with the ratio of CO being less than 1 is generally less than 10MJ/Nm3The CO content is generally 20-40%, and if the fuel gas is directly used as town gas, the problem that the calorific value is low and the CO content of toxic and harmful gas is too high obviously exists.
In order to make the above-mentioned low H2the/CO biomass gas meets the requirements of heat value and CO content in the standard, and is solved by adopting water-gas shift and methanation processes on the technical route. The traditional technological processes of coal-based natural gas and CO removal by synthetic ammonia refining all use a method of connecting water-gas shift and methanation reaction units in series, and have the disadvantages of large equipment investment, complex technological process, low controllability and more influencing factors. If the water-gas shift reaction unit and the methanation reaction unit are integrated, the energy consumption of the system can be reduced, the process flow can be simplified, and the equipment investment can be saved. Therefore, it is important to develop a catalyst with dual functions of shift and methanation.
The existing and industrially used catalysts are mostly catalysts with single functions of methanation and shift, while the catalysts with double functions of shift methanation are less reported in public. CN105925328A discloses a production process for preparing natural gas by sulfur-tolerant shift-methanation of a high-CO-content feed gas, wherein a cobalt-molybdenum-series sulfur-tolerant shift methanation catalyst is used in a first reactor and a second reactor, the catalyst takes magnesium aluminate spinel as a carrier, cobalt oxide and molybdenum oxide as active components, and cerium oxide as an active auxiliary agent. However, the preparation method of the catalyst is tedious and time-consuming, steam curing is required for 10-12 hours only for preparing the magnesia-alumina spinel carrier, and the catalyst is only suitable for sulfur-containing crude gas, needs to be presulfurized when in use and is not suitable for a biomass gas system. In addition, the prior art adopts the traditional roasting mode when preparing the catalyst, takes 3 to 4 hours, and prolongs the preparation period of the catalyst to a certain extent.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a biomass gas shift methanation bifunctional catalyst and a preparation method thereof, and the catalyst is particularly suitable for low H2the/CO biomass fuel gas has the characteristic of simple preparation process on the premise of keeping higher conversion and methanation activity.
The technical scheme is as follows: the invention relates to a shift methanation catalyst, which comprises an active component, an auxiliary agent and a carrier; the active components comprise a first active component nickel and a second active component manganese; the first active component nickel accounts for 5-30% of the mass of the catalyst according to the mass of the metal element; the second active component manganese accounts for 1-10% of the mass of the catalyst according to the mass of the metal element; the assistant is rhenium, and the mass percent of the assistant and the catalyst is 0.2-1.5% by mass of the metal element.
In the catalyst, the mass percent of the first active component nickel and the catalyst is 15-20% by mass according to the mass of the metal element; the second active component manganese accounts for 3-5% of the mass of the catalyst according to the mass of the metal element; the assistant is rhenium, and the mass percentage of the assistant and the catalyst is 1-1.5% by mass based on the mass of the metal element.
The carrier is gamma-Al2O3As the remaining component of the catalyst. The invention adopts gamma-Al2O3The catalyst is a carrier, nickel and manganese respectively have catalytic activity for methanation and water-vapor shift reaction, and meanwhile, the catalyst has better shift methanation synergistic catalytic action by adopting nickel and manganese as active double components, and the catalyst is added with a proper amount of rare dispersion element rhenium as an auxiliary agent to further improve the shift methanation activity and stability of the catalyst.
The gamma-Al2O3White spherical particles with the diameter of 2-3mm, the bulk density of 0.70-0.80g/mL, and the specific surface area of more than or equal to 300m2The pore volume is 0.4 mL/g.
The preparation method of the catalyst of the invention can adopt different preparation methods, such as a ball milling method and the like, according to different existing forms of nickel, manganese and rhenium. The inventors, when studying the catalytic performance of the catalyst, found that impregnation was usedThe catalyst prepared by the method has more excellent catalytic activity, and in addition, when the catalyst is prepared by an impregnation method, different preparation steps also influence the activity of the catalyst, so the catalyst can be prepared by adopting the following preparation method: (1) gamma-Al2O3Impregnating with soluble salt solution of rhenium, and then drying; (2) mixing the mixture obtained in the step (1) with carborundum according to the volume ratio of 1:1-2, and roasting; (3) adding the mixture obtained in the step (2) into a mixed solution of soluble salts of nickel and soluble salts of manganese for dipping, then drying, and screening and separating to remove carborundum; (4) and (4) mixing the mixture obtained in the step (3) with carborundum according to the volume ratio of 1:1-2, roasting, and screening to remove the carborundum to obtain a catalyst finished product.
The dipping temperature in the step (1) and the step (3) is 40-80 ℃; the dipping time is 8-12 h.
In the step (2) and the step (4), the roasting is microwave pyrolysis. The roasting temperature is 400-500 ℃; the roasting time is 5-15 min.
The drying method in the steps (1) and (3) can be selected from a drying oven, the drying temperature is 80-120 ℃, and the drying time is 10-24 h.
The catalyst can also be prepared by adopting the following method: (1) gamma-Al2O3Soaking in mixed solution of soluble salt of nickel, soluble salt of manganese and soluble salt of rhenium at 40-80 deg.C for 8-12 hr, and drying; (2) mixing the mixture obtained in the step (1) with carborundum according to the volume ratio of 1:1-2, performing microwave pyrolysis roasting, roasting at the temperature of 400-.
In the different preparation methods, the soluble salt of nickel is nitrate or sulfate of nickel; the soluble salt of manganese is nitrate or sulfate of manganese; the soluble salt of rhenium is ammonium perrhenate.
The carborundum of the invention is green carborundum with the granularity of 24-46 meshes. The carborundum is an inert substance with strong microwave absorption capacity, and the carborundum is added in the invention to enhance the microwave absorption capacity of the catalyst in the microwave roasting stage of the catalyst.
The microwave pyrolysis adopts a microwave pyrolysis furnace, and the power is 0.8-1.5 kW.
The catalyst prepared by the method can be used after being reduced, the reduction method adopts the prior art and can adopt the following steps to carry out reduction: slowly raising the temperature of the catalyst bed to 250 ℃ at the heating rate of 3-5 ℃/min under the nitrogen atmosphere, switching the gas to be the reducing atmosphere of mixing nitrogen and hydrogen, wherein the concentration of hydrogen is 15-25%, simultaneously maintaining the heating rate of 2-4 ℃/min, further raising the temperature of the catalyst bed to 450 ℃, and reducing at constant temperature for 2-4 h.
The specific application conditions of the catalyst are as follows: the pressure is 0.1-1.0MPa, the temperature is 300--1，H2volume/CO ratio of 0.6-1.0, especially for low H2The process of preparing town gas from CO biomass gas.
In the present invention, "%" is a mass percentage unless otherwise specified.
Has the advantages that: the invention has the double functions of shift and methanation, can simultaneously catalyze the water-gas shift reaction and the methanation reaction, and can be integrated in one reaction unit for the process flow needing to be connected with the two reactions in series, thereby simplifying the process flow and reducing the energy consumption of the system; the catalyst of the invention is particularly suitable for low H2The process of preparing town gas from CO biomass gas does not need to convert the raw material gas in advance in the process flow to increase H2a/CO; the catalyst of the invention adopts a microwave roasting mode in the roasting link of the preparation process, the roasting time is greatly shortened compared with the traditional roasting mode, the preparation period of the catalyst is shortened, and the dispersion degree of the active components of the catalyst can be enhanced, thereby further improving the activity and the stability of the catalyst.
Detailed Description
Firstly, the source of raw materials
1. Gamma-Al used in the invention2O3The carrier is white spherical particles with the diameter of 2-3mm, the bulk density is 0.70-0.80g/mL, and the specific surface area is more than or equal to 300m2The pore volume is 0.4 mL/g;
2. the carborundum used by the invention is green carborundum with the granularity of 24-46 meshes;
3. the rest raw materials of the invention are all obtained from the market.
Second, sample preparation
Example 1: taking 74.32g of Ni (NO)3)2·6H2O, 19.54g of Mn (NO) with a mass concentration of 50%3)2Solution and 1.44gNH4ReO4Preparing a mixed solution, and weighing 73.56g of gamma-Al2O3Soaking a carrier in the mixed solution at a constant temperature of 60 ℃ for 12h, drying the carrier in an oven at 110 ℃ for 12h after soaking, uniformly mixing carborundum and a dried catalyst precursor according to a volume ratio of 3:2, transferring the mixture into a microwave pyrolysis furnace with the power of 1.0kW, roasting the mixture at 400 ℃ for 10min, and screening and separating to remove carborundum to obtain Ni-Mn-Re/Al containing 15.0 wt.% of nickel, 3.0 wt.% of manganese and 1.0 wt.% of rhenium according to the mass of metal elements2O3Shift the methanation catalyst.
Example 2: take 1.44g NH4ReO4Adding deionized water to prepare a solution, weighing 73.56g of gamma-Al2O3Soaking the carrier in the solution at a constant temperature of 40 ℃ for 20h, drying the carrier in a drying oven at 120 ℃ for 8h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 2:1, transferring the mixture into a microwave pyrolysis furnace with the power of 0.8kW, and roasting the mixture at 450 ℃ for 10min to obtain rhenium modified gamma-Al2O3Carrier, 74.32g Ni (NO) weight3)2·6H2O and 19.54g of Mn (NO) with a mass concentration of 50%3)2Preparing a mixed solution from the solution, dipping the modified carrier into the mixed solution, dipping for 12h at a constant temperature of 40 ℃, drying for 8h in an oven at 120 ℃, mixing with carborundum according to a volume ratio of 1:2, transferring into a microwave pyrolysis furnace with a power of 0.8kW, roasting for 10min at 450 ℃, screening and separating to remove the carborundum, and obtaining Ni-Mn/Re-Al with 15.0 wt% of nickel, 3.0 wt% of manganese and 1.0 wt% of rhenium according to the mass of metal elements2O3Shift the methanation catalyst.
Example 3: 99.07g of Ni (NO) were taken3)2·6H2O, 32.56g of Mn (NO) with a mass concentration of 50%3)2Solution and 2.16g NH4ReO4Preparing a mixed solution, and weighing 62.74g of gamma-Al2O3Soaking a carrier in the mixed solution at a constant temperature of 60 ℃ for 12h, drying the carrier in an oven at 110 ℃ for 12h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 3:2, transferring the mixture into a microwave pyrolysis furnace with the power of 1.0kW, and roasting the mixture at 400 ℃ for 10min to obtain Ni-Mn-Re/Al with the nickel content of 20.0 wt.%, the manganese content of 5.0 wt.% and the rhenium content of 1.5 wt.%2O3Shift the methanation catalyst.
Example 4: 2.16g of NH were taken4ReO4Adding deionized water to prepare a solution, weighing 62.74g of gamma-Al2O3Soaking the carrier in the solution at a constant temperature of 40 ℃ for 20h, drying the carrier in a drying oven at 120 ℃ for 8h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 2:1, transferring the mixture into a microwave pyrolysis furnace with the power of 0.8kW, and roasting the mixture at 450 ℃ for 10min to obtain rhenium modified gamma-Al2O3The carrier was further weighed with 99.07g of Ni (NO)3)2·6H2O and 32.56g of Mn (NO) with a mass concentration of 50%3)2Preparing the solution into a mixed solution, soaking the modified carrier in the mixed solution, repeating the soaking, drying and microwave roasting processes in the same steps to finally obtain Ni-Mn/Re-Al containing 20.0 wt.% of nickel, 5.0 wt.% of manganese and 1.5 wt.% of rhenium2O3Shift the methanation catalyst.
Example 5: take 0.29g NH4ReO4Adding deionized water to prepare a solution, weighing 94.54g of gamma-Al2O3Soaking the carrier in the solution at a constant temperature of 40 ℃ for 20h, drying the carrier in a drying oven at 120 ℃ for 8h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 2:1, transferring the mixture into a microwave pyrolysis furnace with the power of 0.8kW, and roasting the mixture at 450 ℃ for 10min to obtain rhenium modified gamma-Al2O3Carrier, 24.77g Ni (NO) weight3)2·6H2O and 6.51g of Mn (NO) with a mass concentration of 50%3)2Preparing the solution into mixed solution, soaking the modified carrier in the mixed solution at 40 deg.C for 20 hr, placing in an oven at 120 deg.C after soakingDrying for 8h, uniformly mixing the carborundum and the dried mixture according to the volume ratio of 2:1, transferring the mixture into a microwave pyrolysis furnace with the power of 0.8kW, and roasting at 450 ℃ for 10min to finally obtain Ni-Mn/Re-Al containing 5.0 wt.% of nickel, 1.0 wt.% of manganese and 0.2 wt.% of rhenium2O3Shift the methanation catalyst.
Example 6: 2.16g of NH were taken4ReO4Adding deionized water to prepare a solution, and weighing 42.09g of gamma-Al2O3Soaking the carrier in the solution at a constant temperature of 40 ℃ for 20h, drying the carrier in a drying oven at 120 ℃ for 8h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 2:1, transferring the mixture into a microwave pyrolysis furnace with the power of 0.8kW, and roasting the mixture at 450 ℃ for 10min to obtain rhenium modified gamma-Al2O3The carrier was further weighed with 148.64g of Ni (NO)3)2·6H2O and 65.13g Mn (NO) with a mass concentration of 50%3)2Preparing a mixed solution from the solution, dipping the modified carrier in the mixed solution at 40 ℃ for 20h, drying the mixed solution in an oven at 120 ℃ for 8h after dipping, uniformly mixing carborundum and the dried mixture according to the volume ratio of 2:1, transferring the mixture into a microwave pyrolysis furnace with the power of 0.8kW, and roasting the mixture at 450 ℃ for 10min to finally obtain Ni-Mn/Re-Al with the nickel content of 30 wt.%, the manganese content of 10 wt.% and the rhenium content of 1.5 wt.%2O3Shift the methanation catalyst.
Comparative example 1: taking 74.32g of Ni (NO)3)2·6H2O and 19.54g of Mn (NO) with a mass concentration of 50%3)2The solution was prepared as a mixed solution, and 76.16g of gamma-Al was weighed2O3Soaking a carrier in the mixed solution at a constant temperature of 60 ℃ for 12h, drying the carrier in an oven at 110 ℃ for 12h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 3:2, transferring the mixture into a microwave pyrolysis furnace with the power of 1.0kW, and roasting the mixture at 400 ℃ for 10min to obtain Ni-Mn/Al with the nickel content of 15.0 wt.% and the manganese content of 3.0 wt.%2O3Shift the methanation catalyst.
Comparative example 2: taking 74.32g of Ni (NO)3)2·6H2O and 1.44g NH4ReO4Preparing into mixed solution, and weighing 78.31gγ-Al2O3Soaking the carrier in the mixed solution at a constant temperature of 60 ℃ for 12h, drying the carrier in an oven at 110 ℃ for 12h after soaking, uniformly mixing carborundum and the dried mixture according to a volume ratio of 3:2, transferring the mixture into a microwave pyrolysis furnace with the power of 1.0kW, and roasting the mixture at 400 ℃ for 10min to obtain Ni-Re/Al with 15.0 wt.% of Ni and 1.0 wt.% of Re2O3Shift the methanation catalyst.
Comparative example 3: taking 74.32g of Ni (NO)3)2·6H2O is prepared into solution, and 80.91g of gamma-Al is weighed2O3Soaking a carrier in the solution at a constant temperature of 60 ℃ for 12h, drying the carrier in an oven at 110 ℃ for 12h after soaking, uniformly mixing carborundum and the dried catalyst mixture according to a volume ratio of 3:2, transferring the mixture into a microwave pyrolysis furnace with the power of 1.0kW, and roasting the mixture at 400 ℃ for 10min to obtain Ni/Al containing 15.0 wt.% of Ni2O3Shift the methanation catalyst.
Comparative example 4: taking 74.32g of Ni (NO)3)2·6H2O, 19.54g of Mn (NO) with a mass concentration of 50%3)2Solution and 1.44gNH4ReO4Preparing a mixed solution, and weighing 73.56g of gamma-Al2O3Soaking the carrier in the mixed solution at a constant temperature of 60 ℃ for 12h, drying in an oven at 110 ℃ for 12h after soaking, and roasting in a muffle furnace for 4h after drying to obtain Ni-Mn-Re/Al containing 15.0 wt.% of Ni, 3.0 wt.% of Mn and 1.0 wt.% of Re2O3Shift the methanation catalyst.
Third, evaluation of catalyst
The catalysts prepared above were subjected to result evaluation, wherein the catalytic effects of examples 5 and 6 were similar to those of the catalyst prepared in example 2, so that the catalysts prepared in examples 1 to 4 and the catalysts prepared in comparative example were subjected to evaluation of the shift methanation catalytic effect, and the catalysts prepared above were reduced by the reduction steps of: slowly raising the temperature of the catalyst bed to 250 ℃ at the heating rate of 3-5 ℃/min under the nitrogen atmosphere, switching the gas to be the reducing atmosphere of mixing nitrogen and hydrogen, wherein the concentration of hydrogen is 15-25%, simultaneously maintaining the heating rate of 2-4 ℃/min, further raising the temperature of the catalyst bed to 450 ℃, and reducing at constant temperature for 2-4 h.
Catalyst evaluation conditions: 50mL of catalyst is filled, the reaction pressure is 0.1MPa, the temperature is 350 ℃, and the gas volume space velocity is 2000h-1The dry gas is mixed gas, wherein CO212% by volume, N28% by volume, H2The total volume of the + CO is 80 percent, and the water vapor H is added2The catalyst was placed in a fixed bed apparatus, reduced, and activity was evaluated, and the results are shown in table 1.
TABLE 1 catalytic Effect of samples on biomass gas shift methanation
Figure BDA0001496294650000061
As can be seen from the comparison of the results of the example 1 and the example 2 and the results of the example 3 and the example 4, the catalysts with the same components prepared by different preparation steps have different catalytic effects, and the methane selectivity of the example 2 and the example 4 is higher. It can be seen from comparative example 1 that rhenium can significantly improve methane selectivity and the calorific value of fuel gas, and the preparation period of the catalyst can be greatly shortened by adopting microwave pyrolysis in the present invention.

Claims (5)

1. The application of the catalyst in catalyzing water-gas shift reaction and methanation reaction simultaneously is characterized in that the catalyst comprises an active component, an auxiliary agent and a carrier; the active components comprise a first active component nickel and a second active component manganese; the first active component nickel accounts for 15-20% of the mass of the catalyst according to the mass of the metal element; the second active component manganese accounts for 3-5% of the mass of the catalyst according to the mass of the metal element; the assistant is rhenium, and the mass percent of the assistant and the catalyst is 1-1.5% by mass of the metal element; the carrier is gamma-Al2O3(ii) a The catalyst is prepared by the following steps: (1) gamma-Al2O3Impregnating with soluble salt solution of rhenium, and then drying; (2) mixing the mixture obtained in the step (1) with carborundum according to the volume ratio of 1:1-2, and bakingFiring in a microwave pyrolysis mode; (3) adding the mixture obtained in the step (2) into a mixed solution of soluble salts of nickel and soluble salts of manganese for dipping, then drying, and screening and separating to remove carborundum; (4) and (4) mixing the mixture obtained in the step (3) with carborundum according to the volume ratio of 1:1-2, roasting in a microwave pyrolysis mode, and screening to remove the carborundum to obtain a catalyst finished product.
2. Use according to claim 1, wherein said γ -Al is2O3Is white spherical particles with the diameter of 2-3mm, the bulk density is 0.70-0.80g/mL, and the specific surface area is more than or equal to 300m2The pore volume is 0.4 mL/g.
3. Use according to claim 1, wherein the soluble salt of nickel is a nitrate or sulphate of nickel; the soluble salt of manganese is nitrate or sulfate of manganese; the soluble salt of rhenium is ammonium perrhenate.
4. The use according to claim 1, wherein the temperature of the impregnation in steps (1) and (3) is 40-80 ℃; the dipping time is 8-12 h.
5. The method as claimed in claim 1, wherein the roasting temperature in steps (2) and (4) is 400-500 ℃; the roasting time is 5-15 min.
CN201711274743.8A 2017-12-06 2017-12-06 Biomass gas shift methanation bifunctional catalyst and preparation method thereof Active CN108144627B (en)

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